Vinyl ethers

ABSTRACT

Compounds of the formula ##SPC1## 
     Wherein X is halogen or hydroxy; R 3  and R 4  represent halogen radicals; and R 5  represents a hydrogen atom or the cyano radical. These compounds are used in the preparation of pesticidal cyclopropane carboxylates.

This invention relates to novel esters, to processes for preparing them,to compositions comprising them, and to methods of combating insectpests using them.

Accordingly the present invention provides esters of formula: ##SPC2##

Wherein R¹ and R² represent halogen radicals or lower alkyl groups; R³and R⁴ represent halogen radicals; and R⁵ represents a hydrogen atom orthe cyano radical.

By the term "halogen" as used herein is meant fluorine, chlorine orbromine; and by the term lower alkyl group is meant an alkyl groupcontaining up to four carbon atoms.

In a preferred form the invention provides compounds wherein R¹ and R²are both methyl groups, or both chlorine radicals, or both bromineradicals. An especially preferred group of compounds within theinvention are those wherein R¹, R², R³ and R⁴ are all chlorine radicals.

It will be readily appreciated that the compounds of the invention asset out hereinabove are described without reference to theirstereochemical nature. Thus the above formula does not differentiatebetween the cis and trans geometrical isomers which are possible due tothe substitution pattern around the cyclopropane ring, nor does itdifferentiate between the various stereoisomeric forms which may bepresent, and the present invention includes within its scope all suchgeometric and optical stereoisomers. Thus the term "compound" as usedherein in relation to esters of the invention refers both to anindividual isomer in isolation, and to mixtures of isomers thereof e.g.racemic mixtures, diastereoisomeric mixtures.

The following compounds are typical examples of compounds according tothe invention.

3(2,2-dichlorovinyloxy)benzyl (±) cis/trans-chrysanthemate (hereinafterreferred to as Compound 1).

3(2,2-dichlorovinyloxy)benzyl (±)cis/trans-2(2,2-dichlorovinyl)3,3-dimethylcyclopropane carboxylate(hereinafter referred to as Compound 2).

3(2,2-dichlorovinyloxy)benzyl (±)cis-2(2,2-dichlorovinyl)-3,3-dimethylcyclopropane carboxylate(hereinafter referred to as Compound 3).

3(2,2-dichlorovinyloxy)benzyl (±)trans-2(2,2-dichlorovinyl)-3,3-dimethylcyclopropane carboxylate(hereinafter referred to as Compound 4).

(±)α-cyano-3(2,2-dichlorovinyloxy)benzyl (±)cis/trans-2(2,2-dichlorovinyl)3,3-dimethylcyclopropane carboxylate(hereinafter referred to as Compound 5).

(±)α-cyano-3(2,2-dichlorovinyloxy)benzyl (±)cis-2(2,2-dichlorovinyl)3,3-dimethylcyclopropane carboxylate.

(-)α-cyano-3(2,2-dichlorovinyloxy)benzyl (±)cis-2(2,2-dichlorovinyl)3,3-dimethylcyclopropane carboxylate.

3(2,2-dichlorovinyloxy)benzyl (±)cis/trans-2(2,2-dibromovinyl)3,3-dimethylcyclopropane carboxylate.

3(2,2-dibromovinyloxy)benzyl (±) cis/trans-chrysanthemate.

3(2,2-dibromovinyloxy)benzyl (±)cis/trans-2(2,2-dichlorovinyl)3,3-dimethylcyclopropane carboxylate.

(±)α-cyano-3(2,2-dichlorovinyloxy)benzyl (±) cis/trans-chrysanthemate.

(±) α-cyano-3(2,2-dichlorovinyloxy)benzyl (±)cis/trans-2(2,2-dibromovinyl)3,3-dimethylcyclopropane carboxylate.

The invention compounds may be prepared by several different processes.Thus a compound of formula:- ##STR1## optionally in the form of a metalsalt thereof, may be reacted with a compound of formula: ##SPC3##

wherein X is a halogen atom, preferably a chlorine or bromine atom, andR¹, R², R³, R⁴ and R⁵ have any of the meanings given hereinabove.Alternatively a compound of formula: ##STR2## may be reacted with acompound of formula: ##SPC4## wherein Y is a halogen atom, preferably achlorine atom, and R¹, R², R³, R⁴ and R⁵ have any of the meanings givenhereinbefore.

In another process the invention esters may be obtained by the processof transesterification wherein the mixture of a simple ester (e.g. alower alkyl ester such as the methyl or ethyl ester) of the acid offormula II and the alcohol of formula V is heated in a solvent ordiluent, preferably in the presence of a base (e.g. a lower alkoxidesuch as sodium methoxide or ethoxide).

These processes may in some cases be carried out by heating thereactants together in the absence of a diluent and/or a base, butpreferably a solvent or diluent and a base is present. Suitable solventsinclude, for example, non-hydroxylic materials such as aliphatic ketones(e.g. acetone), dimethylformamide, dimethylsulphoxide, sulpholane,acetonitrile and tetrahydrofuran. Of these an aliphatic ketone such as,for example acetone is particularly preferred. Hydroxylated solvents,for example, methanol and ethanol, may be used in certain circumstanceswhen the presence of the hydroxyl group does not interfere with theprogress of the reaction. Suitable bases include sodium hydride(although not when a hydroxylated solvent or diluent is used), alkalimetal carbonates, such as potassium carbonate and alkali metalhydroxides such as potassium hydroxide. The temperature at which thereaction may be carried out will depend upon the choice of reactants,solvent or diluent and base. When acetone and potassium carbonate areused the reaction generally takes place at the ambient temperature.Higher temperatures, up to 100° C, may be employed when other bases areemployed. A typical process consists of dissolving or suspending thereactants in a solvent in the presence of a base. After allowing aperiod of time for the reaction to occur the product may be isolated bythe removal of any insoluble portion by filtration and evaporation ofthe filtrate. The product may be purified by distillation under reducedpressure, or by a suitable chromatographic technique. When it is desiredto produce a single geometrically isomeric form of an invention esterthis may be achieved either by using a pure cis or trans acid or acidderivative of formula II or III above, or by using a cis/trans mixturethereof and separating the required isomer from the mixture of estersproduced by for example a chromatographic technique.

The compounds of formula III and formula V which are used in the aboveprocesses for the preparation of the invention esters are themselvesnovel compounds, and may be prepared by the following processes.

Thus a compound of formula III wherein R⁵ is hydrogen may be preparedfrom a compound of the formula: ##SPC5##

by subjecting them to chemical or electrochemical reductivedehydrohalogenation to give a compound of formula:- ##SPC6##

and thereafter halogenating the methyl group of compound VII to producethe required compound of formula III. Z in formula VI is a halogenradical, and is preferably the same halogen radical as that representedby R³ and R⁴.

Compounds of formula VI may be prepared by a method analogous to that ofvon Hesse and Moll, J. Prakt. Chemie, 1974, 316(2), 304 in whichanhydrous chloral or bromal is reacted with m-cresol in the presence ofan acyl halide.

The electrochemical reduction procedure may be carried out in organicsolvents, for example lower alcohols, such as methanol or ethanol,cyclic ethers such as dioxan or tetrahydrofuran, aliphatic ketones suchas acetone or cyclohexanone, or mixtures of these solvents with water orwater containing strong mineral acids such as sulphuric, hydrochloric orphosphoric acids.

The reduction is believed to occur principally at the cathode with ahigh hydrogen overvoltage, for example a mercury, lead amalgam or leadcathode. The reaction can be conveniently carried out in a cell fittedwith a ceramic or glass fritted diaphragm, a stirrer, a workingelectrode and a reference electrode. The process may be adapted forcontinuous production of the required product by use of a solvent systemwith which the product of the reaction may be extracted, for examplemethylene chloride.

The metallic reductive dehydrohalogenation may be carried out with asuitable reducing medium such as zinc dust and acetic acid.

Halogenation of the compounds of formula VII may conveniently be carriedout with the aid of a source of positive halogen, for example anN-haloimide such as N-bromosuccinimide, or N-chlorosuccinimide. Thecompounds of formula V wherein R⁵ is hydrogen may conveniently beprepared from the corresponding compounds of formula III by, forexample, treating them with an alkali metal hydroxide, or alternativelyconverting them to the corresponding tosylate (p-toluenesulphonate) andsubjecting the tosylate to hydrolysis.

Compounds of formula III wherein R⁵ is hydrogen may be converted to thecorresponding compounds wherein R⁵ is a cyano radical by the process oftreating a compound of formula III wherein R⁵ is hydrogen with a sourceof cyanide ion, e.g. an alkali metal cyanide such as sodium cyanide, andthereafter subjecting the compound of formula: ##SPC7##

thus produced to further halogenation. The reaction with cyanide mayconveniently be performed in a polar aprotic solvent such asdimethylformamide, at an elevated temperature in the range 50° to 100°C. The halogenation step may conveniently be performed in the manneroutlined above for the preparation of compound of formula III wherein R⁵is hydrogen. The compounds of formula V wherein R⁵ is cyano may beobtained from the compounds of formula III where R⁵ is cyano byanalogous processes to those set out above for the correspondingcompounds where R⁵ is hydrogen.

A preferred method for the preparation of compounds of formula V whereR⁵ is cyano is however based on a different approach in which a compoundof formula VII is selectively oxidised to a compound of formula:##SPC8##

and this compound is then converted to its cyanohydrin by reaction withhydrogen cyanide, or, preferably, via the bisulphite compound, withcyanide ion (e.g. sodium cyanide). An alternative process for preparingcompound IX involves the oxidation of compound V where R⁵ is hydrogenwith aluminium isopropoxide and acetone under the conditions of theOppenauer reaction.

In another aspect therefore the invention provides compounds of formulaIII, V, VII, VIII and IX, all useful as intermediates in the preparationof the invention esters of formula I, and processes for the preparationof the said compounds of formula III, V, VII, VIII and IX.

As stated above the invention esters of formula I are useful asinsecticides, and are most conveniently used as such when formulatedinto compositions. In another aspect therefore the invention providesinsecticidal compositions which comprise as an active ingredient aninvention ester of formula I in association with agriculturally andhorticulturally acceptable diluent or carrier materials.

In a preferment of this aspect of the invention the active ingredient isselected from amongst the specifically named esters of the invention setout hereinabove.

The compositions are for use in agriculture or horticulture but the typeof composition used in any instance will depend upon the particularpurpose for which it is to be used.

The compositions may be in the form of granules or powders comprisingthe active ingredient and a solid diluent or carrier. The compositionsmay also be in the form of liquid preparations to be used as dips orsprays which are generally aqueous dispersions or emulsions.

The compositions to be used as sprays may also be in the form ofaerosols wherein the formulation is held in a container under pressurein the presence of a propellant such as fluorotrichloromethane ordichlorodifluoromethane.

For agricultural or horticultural purposes, an aqueous preparationcontaining between 0.0001% and 1.0% by weight of the active ingredientor ingredients may be used.

The compositions of the present invention may, if desired, also comprisein addition to a compound of the present invention, at least one otherbiologically active ingredient, for example, an insecticide or afungicide. They may also comprise a synergist of the type useful insynergising the activity of pyrethroids type insecticides.

In use, the invention compounds or compositions may be used to combatinsects in a variety of ways. Thus the insects themselves, or the locusof the insects or the habitat of the insects is treated with a compoundor a composition according to the invention.

The invention also provides a method of treating plants to render themless susceptible to damage by insects, which comprises treating theplants, or the seeds, corms, bulbs, tubers, rhizomes or otherpropagative parts of the plants, or the medium in which the plants aregrowing with a compound or composition according to the invention.

Thus the compounds of the invention are toxic towards a wide variety ofinsect and other invertebrate pests, including for example thefollowing:

    ______________________________________                                        Tetranychus telarius                                                                            Blatella germanica                                          Aphis fabae       Musca domestica                                             Megoura viceae    Pieris brassicae                                            Aedes aegypti     Plutella maculipennis                                       ______________________________________                                    

The invention is illustrated by the following Examples.

EXAMPLE 1

This Example illustrates the preparation of Compound no. 1.

A mixture of dl-chrysanthemic acid (50:50, cis:trans; 1.2 g),3(2,2-dichlorovinyloxy)benzyl bromide (2.0 g), anhydrous potassiumcarbonate (1.0 g) and acetone (25 ml) was stirred at the ambienttemperature (ca. 18°-22° C) for 18 hours. The insoluble portion wasremoved by filtration and the filtrate evaporated under reduced pressureto yield a residual oil which was dissolved in chloroform and washedwith saturated sodium bicarbonate solution and then with water. Afterdrying the chloroform solution over anhydrous magnesium sulphate thesolvent was removed under reduced pressure and the residual oilsubjected to preparative thin layer chromatography using a mixture ofchloroform (10% v/v) and petroleum ether (boiling range 40°-60° C; 90%v/v) as eluent. The required product was identified by infra-red andnuclear magnetic spectroscopy.

EXAMPLE 2

This Example illustrates the preparation of Compound no. 2.

A mixture of dl-3(2,2-dichlorovinyl)2,2-dimethylcyclopropane carboxylicacid (80:20, trans-cis; 0.75 g), 3(2,2-dichlorovinyloxy)benzyl bromide(1.0 g), anhydrous potassium carbonate (0.5 g) and acetone (25 ml) wasstirred at the ambient temperature for 18 hours. The product wasisolated from the reaction mixture by a procedure similar to that usedin Example 1, except that diethyl ether was used in place of chloroformas solvent, and the T.L.C. eluent consisted of 20% v/v chloroform and80% v/v petroleum ether (boiling range 40°-60° C).

EXAMPLE 3

This Example illustrates the preparation of (±)α-cyano-3(2,2-dichlorovinyloxy)benzyl (±)cis/trans-2(2,2-dichlorovinyl)3,3-dimethylcyclopropane carboxylate,Compound no. 5, (Formula I; R¹, R², R², R⁴ are chlorine radicals, R⁵ isa cyano radical).

2(2,2-Dichlorovinyl)3,3-dimethylcyclopropane carboxylic acid (cis/trans(40:60, 1.29 g) is added to thionyl chloride (5.0 g) and the mixtureheated at 100° C (steam bath) for one hour, after which the excessthionyl chloride is removed by azeotropic distillation with toluene. Theresidual acid chloride thus produced is dissolved in n-hexane (3.0 ml)and the solution obtained added dropwise at the ambient temperature to asolution of 3(2,2-dichlorovinyloxy) benzaldehyde cyanohydrin (1.5 g) ina mixture of n-hexane (7.0 ml) and pyridine (0.5 ml). After completingthe addition the mixture is stirred for two hours at the ambienttemperature. The solid precipitate which forms is then removed byfiltration and the filtrate washed with water (2 × 10 ml), dried overanhydrous magnesium sulfate and concentrated by evaporation of thesolvent under reduced pressure. The residual oil is subjected topreparative thin layer chromatography using silica plates and as eluenta mixture of chloroform (2 parts by volume) and petroleum ether (boilingrange 60°-80° C, 3 parts by volume), to yield substantially pure (±)α-cyano-3(2,2-dichlorovinyloxy)benzyl (±)cis/trans-2(2,2-dichlorovinyl)3,3-dimethylcyclopropane carboxylate,consisting of 40% of the cis isomer and 60% of the trans isomer.

EXAMPLE 4

This Example illustrates the preparation of Compounds Nos 3 and 4.

The product obtained by the process of Example 2 (250 mg) was subjectedto preparative thin layer chromatography using a silica coated plate anda solvent mixture comprising 35% v/v chloroform -- 65% v/v petroleumether (60°-80° C). The required products was identified by infra-red andnuclear magnetic spectroscopy as Compound 3 (70 mg; (±) cis-isomer) andCompound 4 (100 mg; (±trans-isomer).

EXAMPLE 5

This Example illustrates the preparation of3(2,2-dichlorovinyloxy)benzyl bromide.

a. Preparation of 1(3-tolyloxy)-2,2,2-trichloroethyl acetate.

To a solution of anhydrous chloral (37.0 g) in dry ether (125 ml) wasadded meta-cresol (27.0 g) and the mixture was stirred at the ambienttemperature for 20 minutes, after which it was cooled to 10° C and asolution of triethylamine (25.25 g) in dry ether (100 ml) was slowlyadded. Acetyl chloride (20.0 g) was then carefully added to the stirredmixture and stirring was continued for one hour. The insoluble materialwas removed by filtration and the filtrate dried over anhydrousmagnesium sulphate. After removal of the ether by evaporation underreduced pressure the residual oil was distilled under high vacuum andthe fraction boiling at 132°-134°/0.5 mm Hg collected. Infra-red andnuclear magnetic spectroscopic analysis indicated that this was1(3-tolyloxy)-2,2,2-trichloroethyl acetate.

b. Preparation of 3-tolyl 2,2-dichlorovinyl ether.

i. By a metallic reductive dehydrohydrogenation method.1(3-tolyloxy)-2,2,2-trichloroethyl acetate (14.2 g) was dissolved inglacial acetic acid (40 ml) and zinc dust (3.6 g) was slowly added tothe solution was stirring at the ambient temperature. The temperaturerose to 60° C in response to the exothermic reaction which occurred,after which the mixture was heated at 50°-60° C for 4 hours. The mixturewas filtered and the filtrate poured in an excess of water and extractedwith chloroform. The extracts were washed twice with water, withsaturated sodium bicarbonate solution, and finally with water. Afterdrying the chloroform extracts over anhydrous magnesium-sulphate, thesolvent was removed by evaporation under reduced pressure and theresidual oil distilled to yield crude 3-tolyl 2,2-dichlorovinyl ether,collected as a fraction boiling at 92°-95° C/0.3 mm, which wasredistilled and the fraction boiling at 84° C/0.2 mm Hg collected.

ii. By an electrochemical reductive dehydrohalogenation method1(3-tolyloxy)-2,2,2-trichloroethyl acetate (15.8 g), concentratedsulphuric acid (98% w/v, 9.8 g) and methanol (220 ml) was charged intoan electrolytic cell, which was surrounded by a cooling bath set tomaintain the temperature at about 15° C, and fitted with a cylindricaldiaphragm, stirrer, reference electrode (SCE) and a working electrode.The cathode was a lead plate (surface area about 40 cm²). Using acurrent density in the range 5 to 10 mA/cm² the reaction was conductedin the potential range -1100 to 1700 mV (SCE). When reduction wascompleted the cathodic electrolyte was neutralised with caustic soda andextracted with methylene chloride, the extracts dried over anhydroussodium sulphate and evaporated to yield a residue of crude 3-tolyl2,2-dichlorovinyl ether.

c. Preparation of 3(2,2-dichlorovinyloxy)benzyl bromide.

3-Tolyl 2,2-dichlorovinyl ether (12.2 g) was dissolved in carbontetrachloride (75 ml), and N-bromosuccinimide (12.0 g) and a trace ofwet benzoyl peroxide added, and the mixture refluxed for 3 hours. Afterfiltration the solvent was evaporated from the filtrate, and the residuedissolved in ether and extracted with 1% w/v sodium hydroxide solution.The ethereal solution was dried over anhydrous magnesium sulphate, thesolvent removed by evaporation under reduced pressure, and the residualoil distilled to yield a fraction boiling a 150° C/0.5 mm Hg. Thisfraction was shown by NMR to contain about 65% of the required producttogether with about 30% of unchanged starting material, the remainderbeing a small proportion of the dibromomethyl compound.

EXAMPLE 6

This example illustrates the preparation of3(2,2-dichlorovinyloxy)benzyl alcohol.

A mixture 3(2,2-dichlorovinyloxy)benzyl bromide (2.8 g), sodiump-toluene sulphonate (2.0 g) and methanol (20 ml) is warmed to 50° C for1 hour, after which water (20 ml) and toluene (20 ml) is added withagitation. The toluene layer is separated, washed with water andconcentrated by evaporation of the solvent under reduced pressure. Theconcentrate is then added dropwise to a 15% (w/v) aqueous solution ofpotassium hydroxide (100 ml) and the mixture warmed to 60° C for 1 hour,cooled to the ambient temperature and extracted with a mixture oftoluene (10 ml) and methyl iso-butylketone (10 ml), the extracts driedover anhydrous magnesium sulphate and the solvents evaporated underreduced pressure to yield 3(2,2-dichlorovinyloxy)benzyl alcohol as aresidual pale yellow oil.

EXAMPLE 7

This Example illustrates the conversion of3(2,2-dichlorovinyloxy)benzaldehyde to its cyanohydrin, via thebisulphite compound.

To a stirred solution of sodium metabisulphite (3.2 g) in a mixture ofwater (5.2 ml) and methanol (5.2 ml) at the ambient temperature is added3(2,2-dichlorovinyloxy) benzaldehyde (2.0 g). After 30 minutes the whiteprecipitate which forms is collected by filtration, washed with coldmethanol and dried to yield the bisulphite compound of3(2,2-dichlorovinyloxy)benzaldehyde (2.5 g). This is suspended in water(5 ml) and to it is added a solution of sodium cyanide (0.4 g) in water(5 ml) at the ambient temperature. The mixture is stirred for 2 hoursand then extracted with diethyl ether (2 × 10 ml). The extracts arecombined, washed with water (2 × 10 ml), dried over an hydrous magnesiumsulphate and evaporated under reduced pressure to yield the cyanohydrinof 3(2,2-dichlorovinyloxy)-benzaldehyde as a yellow oil.

EXAMPLE 8

The activity of a number of the compounds was tested against a varietyof insect and other invertebrate pests. The compounds were used in theform of a liquid preparation containing 0.1% by weight of the compoundexcept in the tests with Aedes aegypti where the preparations contained0.01% by weight of the compound. The preparations were made bydissolving each of the compounds in a mixture of solvents consisting of4 parts by volume of acetone and 1 part by volume of diacetone alcohol.The solutions were then diluted with water containing 0.01% by weight ofa wetting agent sold under the trade name "LISSAPOL" NX until the liquidpreparations contained the required concentration of the compound."Lissapol" is a Trade Mark.

The test procedure adopted with regard to each pest was basically thesame and comprised supporting a number of the pests on a medium whichwas usually a host plant or a foodstuff on which the pests feed, andtreating either or both the pests and the medium with the preparations.

The mortality of the pests was then assessed at periods usually varyingfrom one to three days after the treatment.

The results of the tests are given below in Table I. In this table thefirst column indicates the name of the pest species. Each of thesubsequent columns indicates the host plant or medium on which it wassupported, the number of days which were allowed to elapse after thetreatment before assessing the mortality of the pests, and the resultsobtained for each of the compounds numbered as above. The assessment isexpressed in integers which range from 0-3.

0 represents less than 30% kill

1 represents 30 - 49% kill

2 represents 50 - 90% kill

3 represents over 90% kill

A dash (--) in Table I indicates that no test was carried out.

In Table I `contact test` indicates that both the pests and the mediumwere treated and `residual test` indicates that the medium was treatedbefore infestation with the pests.

                                      TABLE I                                     __________________________________________________________________________                    SUPPORT                                                                             NO. OF                                                                             COMPOUND NO.                                       PEST SPECIES    MEDIUM                                                                              DAYS 1 2 3 4 5                                          __________________________________________________________________________    Tetranychus telarius                                                                          French                                                                              3    1 0 0 1 --                                         (red spider mites, adults)                                                                    Bean                                                          Aphis fabae     Broad 2    3 3 2 0 0                                          (black aphids)  Bean                                                          Megoura viceae  Broad 2    0 3 3 3 2                                          (green aphids)  Bean                                                          Aedes aegypti   Plywood                                                                             1    2 2 3 3 2                                          (mosquito adults)                                                             Musca domestica Milk/ 2    3 3 3 2 3                                          (houseflies - contact test*)                                                                  sugar                                                         Plutella maculipennis                                                         (diamond back moth, larvae)                                                                   Mustard                                                                             2    0 3 3 2 3                                          contact test                                                                  Pieris brassicae                                                              (cabbage white caterpillars -                                                                 Cabbage                                                                             2    3 3 3 3 3                                          contact test)                                                                 Musca domestica Plywood                                                                             2    0 3 3 3 3                                          (houseflies - residual test*)                                                 __________________________________________________________________________

EXAMPLE 9

This Example illustrates a dusting powder which may be applied directlyto plants or other surfaces and comprises 1% by weight of Compound no. 1and 99% by weight of talc.

EXAMPLE 10

25 Parts by weight of Compound no. 2, 65 parts by weight of xylene and10 parts of an alkyl aryl polyether alcohol (`Triton` X-100; `Triton` isa Trade Mark) were mixed in a suitable mixer. There was thus obtained anemulsion concentrate which can be mixed with water to produce anemulsion suitable for use in agricultural applications.

EXAMPLE 11

10 Parts by weight of Compound no. 2, 10 parts of an ethyleneoxide-octylphenol condensate (`Lissapol` NX; `Lissapol` is a Trade Mark)and 80 parts by weight of diacetone alcohol were thoroughly mixed. Therewas thus obtained a concentrate which, on mixing with water, gave anaqueous dispersion suitable for application as a spray in the control ofinsect pests.

"LISSAPOL" NX is a condensate of 1 mole of nonyl phenol with 8 moles ofethylene oxide.

EXAMPLE 12

This Example illustrates the preparation of3(2,2-dichlorovinyloxy)benzaldehyde.

3(2,2-Dichlorovinyloxy)benzyl bromide (2.5 g) was carefully added to astirred solution of hexamethylene tetramine (2.1 g) in carbontetrachloride (20 ml) at the ambient temperature. After five minutes theprecipitate was collected by filtration and washed with acetone. Thesolid thus obtained was added to aqueous acetic acid solution (50% byweight, 16 ml) and the mixture refluxed for one hour. A mixture of water(16 ml) and concentrated hydrochloric acid (4.5 ml) was then added andthe mixture refluxed for a further 15 minutes. After cooling the mixturewas extracted with chloroform, the extracts washed with water (twice),dried over anhydrous magnesium sulphate and the solvent removed byevaporation under reduced pressure to yield a residue of substantiallypure 3(2,2-dichlorovinyloxy)benzaldehyde, identification of which wasconfirmed by infra-red and nuclear magnetic resonance spectroscopy.

We claim:
 1. A compound of formula: ##SPC9##wherein X is halogen orhydroxy; R³ and R⁴ are both the same halogen; and R⁵ is hydrogen orcyano.
 2. A compound according to claim 1 wherein X is hydroxy, R³ andR⁴ are either both chlorine or both bromine and R⁵ is hydrogen or cyano.3. A compound according to claim 1 wherein X is chlorine or bromine, R³and R⁴ are either both chlorine or both bromine, and R⁵ is hydrogen orcyano.
 4. 3(2,2-Dichlorovinyloxy)benzyl bromide. 5.3(2,2-Dichlorovinyloxy)benzyl alcohol. 6.α-Cyano-3(2,2-dichlorovinyloxy)benzyl alcohol.